Graft copolymer of azotic monomer on polyolefin substrate, article thereof, and method of making same



1962 e. w. STANTON ETAL 3,049,508 GRAFT COPOLYMER OF AZOTIC MONOMER ON POLYOLEFIN SUBSTRATE, ARTICLE THEREOF AND METHOD OF MAKING SAME Filed Jan. 29, 1958 IN V EN TORS. George W. 6/0,? fan By Tea 0Q 6. Tray/0r United States Patent Gfiice 3,049,508 Patented Aug. 14, 1962 GRAFT COPOLYMER F AZOTIC MONOMER 0N POLYOLEFIN SUBSTRATE, ARTICLE THEREOF, AND METHOD ()F MAKING SAME George W. Stanton, Walnut Creek, and Teddy G. Traylor,

Concord, Calif., assignors to The Dow Chemical Company, Midland, Mich., a corporation of Delaware Filed Jan. 29, 1958, Ser. No. 711,943 9 Claims. (Cl. 260-455) The present invention lies generally in the field of organic chemistry and contributes in particular to the art which pertains to synthetic, fiber-forming high polymers. More particularly, the present invention has reference to the provision of certain readily-dyeable graft or blocktype copolymers that are comprised of certain azotic monomers, as hereinafter more fully delineated, polymerized on non-aromatic, hydrocarbon, polyolefin polymer substrates which may hereinafter be more simply referred to as polyolefin polymers or merely as polyolefins.

Hydrophobic polymeric materials of varying origin are commonly employed in the manufacture of various synthetic shaped articles including films, ribbons, fibers, filaments, yarns, threads and the like and related structure, which hereinafter Will be illustrated with particular reference to fibers. Non-aromatic, hydrocarbon, polyolefin polymers may be utilized with great advantage for such purposes.

The polyolefin materials that are contemplated as being adapted for utilization as substrates in the practice of the present invention include any of the non-aromatic hydrocarbon olefin polymers, such as polyethylene, polypropylene and the like, that have been prepared from monomeric, non-aromatic hydrocarbon monolefinic monomers containing from 2 to 6 carbon atoms in their molecule, such as ethylene, propylene, 4-methylpentene and the like. It is especially advantageous to utilize a polypropylene composition, particularly one of the fiber-forming variety, for this purpose. In this connection, it is generally desirable for the polyolefin that is employed to be one of the relatively more recent macromolecular, essentially linear high density species of polymers that have become available and which are generally characterized by their essentially linear unbranched molecular configurations, and which may be made under the influence of such catalyst systems as have been described in Belgian Patent No. 533,362 (which are frequently known as being Ziegler-type catalysts). If desired, however, polyethylene may be utilized which is of the conventional, generally branch structured variety that has ordinarily been polymerized under relatively high pressures and is oftentimes referred to and known as being a polythene.

Difiiculty is often encountered in dyeing or coloring synthetic hydrophobic fibers and the like that have been prepared from non-aromatic, hydrocarbon olefin polymers. This is especially so when it is attempted to obtain relatively deeper shades of coloration in the finally dyed product.

Various techniques have been evolved for providing polyolefin compositions of improved dyeability. The practice of such techniques has not always been completely satisfactory. Neither have the products achieved thereby always provided a completely suitable solution to the problems involved. For example, many of the fiber products which are prepared in accordance with the above identified techniques known to the art often have inferior physical properties when they are compared with those prepared from unmodified polyolefin polymers. Also, such products, once they have been prepared, may not be as receptive as might be desired to a wide range of dyestuffs, due to inherent limitations in the materials capable of being employed for enhancing dye-receptivity.

It would be advantageous, and it is the chief aim and concern of the present invention, to provide non-aromatic, hydrocarbon polyolefins which have been modified with certain graft or block copolymerized substituentsso as to be exceptionally dye-receptive while being capable of being fabricated into fibers and the like and related shaped articles having excellent physical properties and other desirable characteristics commensurate with those obtained with the unmodified polyolefin polymer substrates, and of the general order obtainable with polypropylene, for example. This would possibilitate the manufacture of nonaromatic, hydrocarbon polyolefin based fibers and the like articles having the highly desirable combination of attractive physical characteristics and substantial capacity for and acceptance of dyestuffs.

To the attainment of these and related ends, a dyereceptive polymer composition that is adapted to provide shaped articles having excellent physical properties and characteristics while being simultaneously receptive of and dyeable to deep and level shades of coloration with many of a wide variety of dyestufis is, according to the present invention, comprised of a fiber-forming graft or block copolymer which is comprised or consists essentially of a non-aromatic, hydrocarbon polyolefin substrate having a minor proportion of substituents graft copolymerized thereto consisting essentially of polymerized azotic monomers of the varieties hereinafter particularized. Schematically, the compositions may be structurally represented in the following manner:

PYOLPYOL-PYOL-PYOLPYOL- IIIG IIIG IIIG ITIG ITTG wherein the interlinked PYOL symbols represent the polyolefin polymer substrate or trunk and the symbols NG connected thereto the substituent graft copolymer branches of the indicated azotic monomer provided thereon.

As is apparent, the graft copolymer substituent that is combined with the polyolefin polymer substrate lends the desired receptivity of and substantivity for various dyestuffs to the compositions while the non-aromatic, hydrocarbon, polyolefin polymer trunk substrate that is so modified facilitates and secures the excellent physical properties and characteristics of the various shaped articles, in cluding fibers, into which the compositions may be fabricated. Advantageously, as mentioned, the polyolefin polymer substrate that is modified by graft copolymerization to provide the compositions of the invention is polypropylene, particularly that of the fiber-forming variety.

It is usually beneficial, as has been indicated, for the graft copolymer compositions of the present invention to contain a major proportion of the polyolefin polymer trunk or substrate that has been modified with the sub stituent dye-receptive graft copolymer groups chemically attached thereto. As a general rule, for example, it is desirable for the graft copolymer to be comprised of at least about percent by weight of the polyolefin polymer substrate. In many instances, it may be satisfactory for the graft copolymer composition to be comprised of between about and percent by weight of the polyolefin polymer substrate, particularly when it is polypropylene. In this connection, however, better dyeability may generally be achieved when the grafted azotic copolymeric substituents are prepared under such conditions that they have relatively long chain lengths. Thus, it is usually preferable, when identical quantities of grafted substituents are involved for relatively fewer, but longer chain length The azotic monomers which are utilized to modify the non-aromatic hydrocarbon polyolefin polymer substrates so as to provide the graft copolymer compositions of the present invention may be selected from the group consisting of vinyl pyridine monomers of the structural formula:

X N x (I) wherein one X is a vinyl (CH=CH radical and the remanider are independently selected from the group consisting of hydrogen and lower alkyl groups or radicals that contain from 1 to 4 carbon atoms; aminated alkenyl 'a'roma'ticmonorners of the structural formula:

whereinQ is selected from the group consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; R is hydrogen or methyl; X is a halogen of atomic .nuniber from 9 to 53 (i.e., fluorine, chlorine, bromine and iodine); n has a whole number value from to 1; and each G is independently selected from the group consisting ."of hydrogen, methyl, and hydroxyethyl (CH CH OH) radicals; and 'arninated acrylate and methacrylate monoiniers of the structural formula:

whereinX'is selected from the group consisting of hydrogen and methyl radicals and each Ris independently selected from .the group consisting of hydrogen, methyl and ethyl radicals; and mixtures thereof.

v Typical of the various azotic monomers that may be employed with benefit in the practice of the present invention are those included in the following tabulations, grouped according to general type, wherein the advantageoussp'ecies are designated by the symbol (F):

1 Table 1.Typical Vinyl Pyridines of the Formula I 2 -vinyl pyridine (F) 2-vinyl-4-methyl pyridine (F) -4-vinyl pyridine (F) -2,4-diethyl-6-vinyl pyridine -2-methyl-4-vinyl pyridine 2-vvinyl4-tertiarybutyl pyridine As is apparent, the aminated alkenyl aromatic monomers may be utilized in the form of free amines or their halogen salts, particularly their chlorides. If desired, the azotic monomers of the present invention may be utilized in combination or mixture with other varieties of monomers in order to prepare mixed graft copolymers having specific properties and eifects, particularly with respect to their capability for accepting greater numbers of diverse types of dyestufis. For example, the referred to 'varities of azotic monomers generally provide graft copolymers showing excellent acceptance of direct or acid types of dyestuffs. However, other varieties of monomers such as those which may provided acidic chemical characteristics in the resulting graft copolymer structure may frequently be used with great advantage to enhance the dye-receptivity of the resulting product to basic types of dyestuffs. Such monomers as the various sulfonatcd vinyl aromatic monomers; the sulfonated olefin monomers and the sulfonated acrylate and methacrylate monomers may frequently be used in beneficial combination with the azotic monomers contemplated herein.

As mentioned, the graft copolymer compositions of the invention have remarkably good dye-receptivity, particularly in view of their polyolefin polymer origin. In most cases, for example, the dye-receptivity of the graft copolymer compositions of the present invention is improved to such an extent in comparison with unmodified polyolefin polymers, particularly unmodified polypropylene, that a color differential of at least about 40 Judd units, as hereinafter illustrated, may readily be obtained between samples of the unmodified polyolefin polymer substrate and the graft copolymer compositions of the present invention, each of which have been dyed at a 4 percent dyeing, according to conventional techniques with such a 'dyestuff as Calcodur Pink ZBL. This is a significant advantage when the compositions are fabricated into shaped article form, especially when they are prepared in a filamentary form suitable for use as a textile material.

The Judd unit referred to in the foregoing is described and defined by D. B. Judd in an article in the American Journal of Psychology, vol 53, page 418 (1939). More applicable data appears in Summary On Available Information on Small Color Difierence Formulas, by Dorothy Nickerson, in the American Dyestuif Reporter, vol. 33, page 252 (June 5, 1944). See also Interrelation of Color Specifications, by Nickerson, in the Paper Trade Journal, vol. 125, page 153, for November 6, 1947.

As is well known, Calcodur Pink 2BL is direct type of dye that has a Colour Index 353, more recently designated Colour Index Direct Red 75. It is commercially obtainable under the indicated trade-designation. The same dyestufi, which is the sodium salt of 3,3-disulphodiphenyl-urea-4,4-diazobis 2 amino-8-naphthol-6-sulfonic acid, is actually available (frequently under other commercial designations) from several sources. Calcodur Pink 2BL has the following structural formula, asis given on page 88, Section A, Part I of the Colour Index (-lst Ed., 1924) published by the (British) Society of Dyers and Colourists:

l?esides having excellent physical properties and other deslrable characteristics, fibers and the like articles comprised of the present compositions similarly have the indicated high capacity for being readily and satisfactorily dyed to deep and level shades of coloration with many dyestuffs. For example, fibers of the present compositions may be easily and successfully dyed according to conventional procedures using acid, vat, acetate, direct, naphthol, and sulfur dyes. Such dyestuffs, in addition to the particular variety mentioned, by way of didactic illustration, as Calcocid Alizarine Violet (Colour Index 61710, formerly Colour Index 1080), Sulfanthrene Red 3B (Colour Index Vat Violet 2), Amacel Scarlet BS (American Prototype Number 244 and Colour Index Dispersed Red 1 or 11110), Naphthol ASMX (Colour Index 35527), Fast Red TRN Salt (Colour Index Azoic Diazo Component 11) and Immedial Bordeaux G (Colour Index Sulfur Brown 12) may advantageously be employed for such purposes.

Other dyestufis, by way of further illustration, that may be utilized beneficially on the fiber products of the dye-receptive graft copolymer compositions of the in vention include such direct cotton dyes as Chlorantine Fast Green 5BLL (Colour Index Direct Green 27), Chlorantine Fast Red 7B (Colour Index Direct Red 81), Pontamine Green GX Conc. 125 percent (Colour Index Direct Green 6), Calcomine Black EXN Conc. (Colour Index Direct Black 28), Niagara Blue NR (Colour Index Direct Blue 151) and Erie Fast Scarlet 4BA (Colour Index Direct Red 24); such acid dyes as Anthraquinone Green GN (Colour Index Acid Green 25), Sulfonine Brown 2B (Colour Index Acid Orange 51), Sulfonine Yellow 26 (Colour Index Acid Yellow 40), Xylene Milling Black 213 (Colour Index Acid Black 26A), Xylene Milling Blue FF (Colour Index Acid Blue 61), Xylene Fast Rubine 3GP PAT (Colour Index Acid Red 57), Calcocid Navy Blue R Conc. (Colour Index Acid Blue 120), Calcocid Fast Blue BL (Colour Index Fast Blue 59), Calcocid Milling Red 3R (Colour Index Acid Red 151), Alizarine Levelling Blue 2R (Colour Index Acid Blue 51), Amacid A and Yellow G Extra (both Colour Index Acid Yellow 63); such mordantacid dyes as Alizarine Light Green GS (Colour Index Acid Green such vat dyestufifs as Midland Vat Blue R Powder (Colour Index Vat Blue Sulfanthrene Brown G Paste (Colour Index Vat Brown 5), Sulfanthrene Blue 2B Dbl. Paste (Colour Index Vat Blue 5), and Sulfanthrene Red 3B Paste (Colour Index Vat Violet 2); Indigosol Green IB Powder (Colour Index Vat Green 1), a soluble vat dyestuif; such acetate dyes as Celliton Fast Brown 3RA Extra CF (Colour Index Dispersed Orange 5), Celliton Fast Rubine BA CF (Colour Index Dispersed Red 13), Artisil Direct Red SBP and Celanthrene Red 3BR Cone. (both Colour Index Dispersed Red 15), Celanthrene Pure Blue BRS 400 percent (Colour Index Dispersed Blue 1) and Acetamine Yellow N (Colour Index Dispersed Yellow 32); B-Naphthol 2-chloro-4-nitroaniline, an azoic dye; such sulfur dyes as Katigen Brilliant Blue GGS High Conc. (Colour Index Sulf. Blue 9) and Indo Carbon CLFS (Colour Index Sulf. Blue 6); and premetallized dyestuffs including Cibalan Yellow GRL (Colour Index Acid Yellow 116); and the like.

The dyed products, especially textile fiber products, are generally lightfast and are well imbued with good resistance to crocking. A shaped filamentary article prepared from a dye-receptive composition in accordance with the present invention is schematically illustrated in the sole FIGURE of the hereto annexed drawing.

The dye-receptive graft copolymers of the present invention may be prepared and provided by swelling or impregnating the polyolefin polymer substrate with the monomeric substance then polymerizing the monomer in situ in the substrate. Advantageously, this may be accomplished when the substrate is in the form of an already shaped article, such as a fiber or filamentary structure. Beneficially, the graft copolymerization of the impregnated monomer may be accomplished and facilitated with the assistance of a polymerization catalyst or catalyzing influence which preferentially interacts with the substrate in order to establish or form grafting sites thereon and simultaneously or subsequently initiate the graft copolymerization. As a practical matter, it is generally most desirable to form the graft copolymer compositions in such manner. Most of the free radical generating chemical catalysts, including peroxide and persulfate catalysts, and actinic radiations, including ultraviolet light, may be utilized for the desired graft copolymerization. It may often be exceptionally advantageous, however, to accomplish the graft copolymerization by subjecting the monomer-impregnated polyolefin polymer substrate to a field of high energy radiation in order to efiiciently provide an effectively attached graft copolyrner of the polymerized monomeric impregnate on the hydrophobic polyolefin polymer substrate. Excellent results may also be achieved by activating the polyolefinic polymer substrate prior to contact with the monomer so as to generate or create free radical sites upon the substrate to which the monomer may attach in order to form the graft polymerized substituents. Such activation, as is known, may be accomplished by means of pre-irradiation in fields of high energy radiation (including ultraviolet light) or by exposing the polyolefinic polymer substrate to the influence of oxygen (in the presence of ultraviolet light) or to already formed ozone prior to contact with the graft copolymer-forming monomer.

The monomer may be intimately impregnated in the polyolefin polymer substrate in any desired manner prior to the graft copolymerization. Thus, the monomer may be directly applied, particularly when it has a swelling effeet on the substrate, or it may be applied from dispersion or solution in suitable liquid vehicles, preferably those tending to swell the polymer, until a desired monomer content has been obtained. Ordinarily, it is advantageous for the monomer to be diluted in a solvent or dispersant vehicle so as to provide a treating bath in which to swell or impregnate the polyolefin polymer Substrate with the latter being immersed in the bath for a sufficient period of time to attain a desired monomer content adequate for the intended purpose. The polyolefin polymer substrate, as has been mentioned, may be in any fabricated or unfabricated form. Unfabricated graft copolymer compositions in accordance with the present invention may be converted to shaped articles by any desired technique adapted for such purpose with conventional polymers. It is generally desirable and of significant advantage, however, to impregnate a preformed article, such as a textile fiber of the polyolefin polymer (or a cloth or fabric comprised thereof) with the monomer in order to prepare the graft copolymer compositions of the invention.

In this connection, particularly when preformed fiber structures are involved, the article may be in any desired state of formation for the impregnating and graft copolymerizing modification. Thus fibers and film-s may be treated before or after any stretch has been imparted thereto. In addition, they may be in various stages of orientation, or in a gel, swollen or dried condition.

The impregnation and succeeding polymerization may, in general, be effected at temperatures between about 0 C. and about 200 C. for periods of time ranging up to 4 or more hours. The most suitable conditions in each instance may vary according to the nature and quantity of the specific monomeric impregnant involved and the graft copolymerizing technique that is utilized. For example, when chemical catalysts are employed for purposes of forming the graft copolymer, a temperature of between about 50 and C. for a period of time between about 15 and 45 minutes may frequently be advantageously employed for the purpose. Under the influence of high energy radiation, however, it may frequently be of greatest advantage to accomplish the graft copolymer- 7 ization at temperatures between about 20 and 60 C. utilizing relatively low dose rates and total dosages of the high energy for the desired purpose. Graft copolymerization on pre-activated substrates may ordinarily be accomplished by simply exposing the activated substrate to the monomer (preferably in concentrated solution) at an elevated temperature until the graft copolymerized substituents have formed on the substrate.

When the graft copolymer compositions are prepared from preformed or already shaped polyolefin polymer substrates that are successively impregnated with the monomer, which is then graft copolymerized in situ in the shaped article, excess monomer, if desired, may be squeezed out or removed in any suitable manner prior to effecting the graft copolymerization.

The chemical free radical generating catalysts which may be employed with greatest advantage in the preparation of the graft copolymer compositions of the present invention include hydrogen peroxide, benzoyl peroxide, cumene hydroperoxide, ammonium or potassium persulfate and the like. Such catalysts may be used in conventional quantities to effect the graft copolymerization. When they are utilized, it is of greatest benefit to incorporate them in the impregnating solution of the monomer that is used.

The high energy radiation which may be employed for inducing the graft copolymerization for the preparation of the graft copolymers of the present invention is of the type which provides emitted particles or photons having an intrinsic energy of a magnitude which is greater than the planetary electron binding energies that occur in the graft copolymerizing materials. Such high energy radiation is available from various radioactive substances which provide beta or gamma radiation as, for example, radioactive elements including cobalt-60 and cesium-137, nuclear reaction fission products and the like. If it is preferred, however, high energy radiation from such sources as electron beam generators, including linear accelerators and resonant transformers, X-r-ay generators and the like may also be utilized. It is beneficial to employ the high energy radiation in a field of at least Iare fully utilized and the wall effect of the chamber is avoided).

It is most desirable, incidentally, to graft copolymerize all or substantially all of the monomeric impregnant to and with the acrylonitrile polymer substrate being modified in order to provide the compositions of the present invention. In addition, as has been indicated, particularly when preactivation of the substrate is performed, ultraviolet light may also be employed as the high energy radiation form, including its use in combination with oxygen or ozone.

For purposes of specifically illustrating, without intending to thereby limit the invention, the following didactic examples are provided wherein, unless otherwise indicated, all parts and percentages are to be taken by weight.

Example 1 A sample of polypropylene fine fiber having a size of about 3 denier was ozonated in order to cause activation of free radical sites on the polymer by subjecting it at room temperature for about one hour to a stream of oxygen that contained ozone in the amount of 26 percent. The ozone was generated by passing oxygen through a 7500 volt electric arc. The fiber was made by melt spinning polypropylene having an apparent molecular weight of about 200,000 (as determined by viscosity) and a melting point of about 170 C. After being ozonpolypropylene fiber.

ated, the fiber was heated for 4 hours at 100 C. in 2- vinyl pyridine. After treatment in the monomer, the graft copolymer fiber product was removed, washed thoroughly with water, and dried. The graft copolymerized fiber product was then dyed with Calcodur Pink 2BL. A deep red shade of coloration was obtained. In contrast, the unmodified yarn could be dyed to only the faintest degree with the same dyestuff.

The graft copolymerized fiber product was also dyed well to deep and level shades of coloration with Calcocid Alizarine Violet, an acid type of dyestutf (Color Index 1080); and Amacel Scarlet BS, an acetate type of dyestulf (American Prototype No. 244). Its reflectance value (as hereinafter defined) upon a 4 percent dyeing in the usual manner with Calcodur Pink 2BL was about The dyeing with Calcodur Pink ZBL was performed at the 4 percent level according to the usual procedure in which the fiber sample was maintained for about one hour at the boil in the dyebath which contained the dyestufi in about an amount equal to about 4 percent of the weight of the fiber. The dyebath also contained sodium sulfate in an amount equal to about 15 percent of the weight of the fiber and had a bath-to-fi-ber weight ratio of 30:1. After being dyed, the fiber was rinsed in water and dried for about 20 minutes at C. The dye-receptivity of the Calcodur Pink ZBL-dyed fiber was evaluated spectrophotometrically by measuring the amount of monochromatic light having a wave length of about 520 millimicrons from a standard source that was reflected from the dyed sample. The numerical value obtained was taken along an arbitrarily designated scale from 0 to l00. This value represented the relative comparison of the light that Was-reflected from a standard white tile reflector that had a reflectance value of 316 by extrapolation from the 0 to scale. Lower reflectance values are an indication of better dye-receptivity in the fiber. For example, a reflectance value of about 20 to 50 for polyolefin polymer fibers dyed with 4 percent Calcodur Pink 23L is generally considered lby those skilled in the art to represent a degree of dye-receptivity that readily meets or exceeds the most rigorous practical requirements and is ordinarily assured of receiving general commercial acceptance and approval. Ordinary unmodified polypropylene fibers of the same type used for the preparation of the graft copolymerized product generally have a reflectance value of about on the same numerical scale. Thus the improvement in dye-receptivity between the graft copolymerized fiber product of the present invention in comparison with unmodified polypropylene was such that a color differential of about 30 Judd units was obtained between the dyed graft copolymer composition and the unmodified Example 2 The procedure of Example 1 was repeated with the exception that the ozonated fiber was treated in a 10 percent solution of dimethylaminoethyl acrylate in N-methyl pyrrolidone. Good dyeability was achieved with Calcodur Pink 2BL and other dyestuffs on the graft copolymerized fiber product.

Example 3 The procedure of the first example was repeated with .the exception that the ozonated fiber was treated in an melting point was 157 and 167 C., respectively.

Example 4 The procedure of Example 1 is duplicated excepting to accomplish the graft copolymerization under the influence 9 of an electron beam from a Van de Graaf generator (instead of the ozone) operated at 2 million electron volts to effect a total dosage of about 10 mrep. at a dose rate of about 5 mrep. per minute. Identical results are obtained.

Results similar to the foregoing may also be obtained when any other of the mentioned varieties of azotic monomers of the Formulae I, II and III are utilized in a similar manner in place of those set forth in the above examples and when graft copolymers are prepared with such monomers on unfabricated forms of the polymer substrate or when the monomers are utilized with other varieties of nonaromatic, hydrocarbon olefin polymers.

What is claimed is:

l. Dye-receptive graft copolymer composition comprised of (l) a polyolefin of a 2 to 6 carbon atom, nonaromatic, monoolefin, said polyolefin substrate having chemically attached thereto to carbon atoms in its chain, as graft copolymerized substituents thereon, a minor proportion of up to about 20 percent by weight, based on the weight of the composition, of units consisting of (2) a polymerized azotic monomer selected from the group consisting of cinyl pyridine monomers of the structural formula:

wherein one X is a vinyl (-CH=CH radical and the remainder are independently selected from the group consisting of hydrogen and lower alkyl radicals that contain rom 1 to 4 carbon atoms; aminated alkenyl aromatic monomers of the structural formula:

CH2=CR CHz-NGKRX);

wherein Q is selected from the group consisting of hydrogen and alkyl radicals containing from 1 to 4 carbon atoms; R is selected from the group consisting of hydrogen and methyl; X is a halogen; n has a whole numerical value from to 1; and each G is independently selected from the group consisting of hydrogen, methyl, and hydroxyethyl (-CH CH OH) radicals; and aminated acrylate and methacrylate monomers of the structural formula:

CH =CXCOOCH CH NR wherein X is selected from the group consisting of hydrogen and methyl radicals and each R is independently selected from the group consisting of hydrogen, methyl and ethyl radicals; and mixtures thereof.

2. The composition of claim 1, wherein said polyolefin substrate has between about 5 and 15 percent by weight, based on the Weight of the composition, of said graft copolymerized substituents attached thereto.

3. The composition of claim 1, wherein said polyolefin substrate is polypropylene.

4. The composition of claim 1, wherein said graft copolymerized substituents are comprised of polymerized 2-vinyl pyridine.

5. The composition of claim 1, wherein said graft copolymerized substituents are comprised of polymerized dimethyl aminoethyl acrylate.

6. The composition of claim 1, wherein said polyolefin substrate is polypropylene and wherein said graft copolymerized substituents are present in an amount up to about 20 percent by weight, based on the weight of the composition, and are comprised of polymerized 2-vinyl pyridine.

7. A filamentary shaped article comprised of the composition set forth in claim 6.

8. A filamentary shaped article comprised of the composition set forth in claim 1.

9. Method for the preparation of a dye-receptive graft copolymer which consists essentially of contacting an un modified polymer of a 2 to 6 carbon atom, non-aromatic monoolefin with a monomer selected from the group consisting of vinyl pyridine monomers of the structural formula:

wherein one X is a vinyl (CH=CH radical and the remainder are independently selected from the group consisting of hydrogen and lower alkyl radicals that contain from 1 to 4 carbon atoms; aminated alkenyl aromatic monomers of the structural formula:

wherein Q is selected from the group consisting of hydro gen and alkyl radicals containing from 1 to 4 carbon atoms; R is selected from the group consisting of hydro gen and methyl; X is a halogen; n has a whole numerical value from 0 to 1; and each G is independently selected from the group consisting of hydrogen, methyl, and hydroxyethyl (CH CH OH) radicals; and aminated acrylate and methacrylate monomers of the structural formula:

CH =CXCOOCH CH NR wherein X is selected from the group consisting of hydrogen and methyl radicals and each R is independently selected from the group consisting of hydrogen, methyl and ethyl radicals and mixtures thereof; then polymerizing said monomer in contact with said polymer at a temperature between about 0 C. and about 200 C. until said monomer is graft copolymerized on said polymer.

References Cited in the file of this patent UNITED STATES PATENTS 2,538,779 Harrison Jan. 23, 1951 2,688,008 Chaney Aug. 31, 1954 2,837,496 Vandenberg June 3, 1958 FOREIGN PATENTS 781,434 Great Britain Aug. 21, 1957 

1. DYE-RECEPTIVE GRAFT COPOLYMER COMPOSITION COMPRISED OF (1) A POLYOLEFIN OF A 2 TO 6 CARBON ATOM, NONAROMATIC, MONOOLEFIN, SAID POLYOLEFIN SUBSTRATE HAVING CHEMICALLY ATTACHED THERETO TO CARBON ATOMS IS ITS CHAIN, AS GRAFT COPOLYMERIZED SUBSTITUENTS THEREOF, A MINOR PROPORTION OF UP TO ABOUT 20 PERCENT BY WEIGHT, BASED ON THE WEIGHT OF THE COMPOSITION, OF UNITS CONSISTING OF (2) A POLYMERIZED AZOTIC MONOMER SELECTED FROM THE GROUP CONSISTING OF CINYLY PYRIDINE MONOMERS OF THE STRUCTURAL FORMULA: 